This study was performed in two phases of work.In the first stage,four conventional first-order flotation kinetics models were fitted to the measured recoveries data and the best model were selected.In the second stag...This study was performed in two phases of work.In the first stage,four conventional first-order flotation kinetics models were fitted to the measured recoveries data and the best model were selected.In the second stage,influence of pH,solid concentration,water chemistry and the amount of collector dosage were investigated on kinetics parameters including flotation rate constant and ultimate recovery.The results indicated that that perfectly mixed reactor model and Kelsall model gave the best and the weakest fit to the experimental data,respectively.It was observed that flotation rate constant and ultimate recovery were strongly affected by chemical factors investigated especially water quality.The flotation rate constant decreased with increasing the solids content,while ultimate recovery increased to certain value and thereafter reduced.It was also found that the most values of flotation rate constant and ultimate recovery obtained in dosage of collector are 30 and 40 g/t,respectively.展开更多
The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12](tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated ...The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12](tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated using a constant interfacial cell with laminar flow. The effects of stirring speed, temperature and specific interfacial area on the extraction rate were examined. The results indicate that mass transfer kinetics of La(III) is a mixed-controlled process influenced by interfacial reaction. On the basis of mass transfer kinetic results in the extraction of La(III) by [A336][CA-12], the extraction rate equation of La(III) is proposed in terms of pseudo-firstorder constants, which is supported by the measured thermodynamic equations. The mass-transfer kinetic model deduced from the rate controlling step is adequate to interpret the experimental data qualitatively.展开更多
Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents c...Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents causes problems such as slow crystallization rate and small crystal size,limiting the recovery rate and economic value of the MAP.The present study was conducted to investigate the effects of concentrations of three heavy metal ions(Cu^(2+),Zn^(2+),and Pb^(2+))on the crystal morphology,crystal size,average growth rate,and crystallization kinetics of MAP.A relationship was established between the kinetic rate constant Ktcalculated by the chemical gradient model and the concentrations of heavy metal ions.The results showed that low concentrations of heavy metal ions in the solution created pits on the MAP surface,and high level of heavy metal ions generated flocs on the MAP surface,which were composed of metal hydroxides,thus inhibiting crystal growth.The crystal size,average growth rate,MAP crystallization rate,and kinetic rate constant Ktdecreased with the increase in heavy metal ion concentration.Moreover,the Ktdemonstrated a linear relationship with the heavy metal concentration ln(C/C~*),which provided a reference for the optimization of the MAP crystallization process in the presence of heavy metal ions.展开更多
A novel constant interfacial area cell(NCIAC),by spatially separating the agitation from liquid flow circulation of organic and aqueous two phases,was suggested to obtain detailed kinetic data for Er(Ⅲ) extraction fr...A novel constant interfacial area cell(NCIAC),by spatially separating the agitation from liquid flow circulation of organic and aqueous two phases,was suggested to obtain detailed kinetic data for Er(Ⅲ) extraction from chloride medium by 2-ethyl-hexyl-phosphonic acid mono-(2-ethylhexyl) ester(EHEHPA).Different from the traditional Lewis cell and the constant interfacial area cell with laminar flow,the concentrations of Er(Ⅲ) in organic and aqueous two phases were uniform,and the stability of the interfacial area between the two phases could be controlled effectively.Therefore,the special requirements for the design of agitators in the traditional Lewis cell and the constant interfacial area cell for minimizing the influence of diffusion resistance could be avoided.Experimental results indicated that the extraction kinetics was mainly affected by the aqueous flow rate,interfacial area between organic and aqueous two phases,and the aqueous p H values.An extraction kinetic equation was suggested based on the experimental data.展开更多
A technique was developed to study mass trans fer process and inter facial reaction in two phases system. This constant inter facial cell with a laminar flow was made into a cubic structure. The two fluids were contin...A technique was developed to study mass trans fer process and inter facial reaction in two phases system. This constant inter facial cell with a laminar flow was made into a cubic structure. The two fluids were continuously recycled and mixed. The concentration of each liquid could be monitored by two different methods. This kind of structure made both flows near the inter face flow parallel to the inter face. The inter face was smooth and steady. The mass trans fer rate could be judged by the linear velocity of the flows. The technique can be used for the analyses of the control step in both phases near the inter face in a diffusion control process. A preliminary hydrodynamics and mass trans fer study on the cell was presented, which ensures the distinguishing between a diffusion and a chemical reaction control process. A simplified mass transfer equation,N =0.5303D 1 /2* (Ci- Cb)* (V / B) 1/2, was achieved.展开更多
The extraction kinetics of Ce(Ⅳ) and Ce(Ⅳ)-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]([trialkylmethylammonium][di-2-ethylhewanxylphosphinate]) with a const...The extraction kinetics of Ce(Ⅳ) and Ce(Ⅳ)-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]([trialkylmethylammonium][di-2-ethylhewanxylphosphinate]) with a constant interfacial area cell with laminar flow were studied,just to elucidate the extraction mechanism and the mass transfer models.The data were analyzed in terms of pseudo-first-order constants.The effects of stirring speed,specific interfacial area and temperature on the extraction rate in both systems were discussed,suggesting that the extractions were mixed bulk phases-interfacial control process.Supported by the experimental data,the corresponding rate equations for Ce(Ⅳ) extraction system and Ce(Ⅳ)-F^- mixture extraction system were obtained.The experimental results indicated the rate-controlling step.The kinetics model was deduced from the rate-controlling step and consistent with the rate equation.展开更多
Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of...Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism: (a) 700-750°C, (b) 750-800°C, and (c) 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000°C), the dominant controlling mechanism is diffusion.展开更多
The kinetics of the catalytic reforming reaction of methane with carbondioxide to produce synthesis gas on a Ni/α-Al_2O_3 and a HSD-2 type commercial catalyst has beenstudied. The results indicate that the reaction o...The kinetics of the catalytic reforming reaction of methane with carbondioxide to produce synthesis gas on a Ni/α-Al_2O_3 and a HSD-2 type commercial catalyst has beenstudied. The results indicate that the reaction orders are one and zero for methane and carbondioxide, respectively, when the carbon dioxide partial pressure was about 12.5-30.0 kPa and thetemperature was at 1123-1173 K. However, when the carbon dioxide partial pressure was changed to30.0-45.0 kPa under the same temperature range of 1123-1173 K, the reaction orders of methane andcarbon dioxide are one. Furthermore, average rate constants at different temperatures weredetermined.展开更多
Objective To investigate the kinetic rate constants ozone and hydroxyl radicals towards two groups of antimicrobials --sulfadiazine (SD) and sulfamethoxazole (SMX).Methods The solute consumption method was used to...Objective To investigate the kinetic rate constants ozone and hydroxyl radicals towards two groups of antimicrobials --sulfadiazine (SD) and sulfamethoxazole (SMX).Methods The solute consumption method was used to detect the rate constants of ozone alone with sulfadiazine and sulfamethoxazole, and tertiary butanol was selected as a scavenging agent and pH was adjusted to 2.5 by adding orthophosphate buffers (OB); and the competition kinetics studying methodwith nitrobenzene as a reference was applied to measure the rate constants of hydroxyl radicals towards sulfadiazine and sulfamethoxazole, and oH was adjusted to 7.0 bv adding OB.Results The rate constants of SD and SMX with ozone alone were 261 mol^-1· dm^3 · s^-1 and 303 mol^-1· dm3 · s-1 by calculating in low reaction system. The rate constants of hydroxyl radicals with SD and SMX were 2.2×1010 mol^-1 · dm^3 · s^-1 and 2.7×1010 mol^-1· dm^3 · s^-1, respectively. Moreover, the rate constants of hydroxyl radicals with SMX were found to have increased from 3.6×109 mol^-1· dm^3 · s^-1 to 2.8×1010 mol^-1· dm^3 · s^-1 with pH value rising from 5.0 to 7.8. Conclusion SMX and SD are both refractory to ozone oxidation alone, and are liable to be degraded by hydroxyl radicals, and the rate constants of SMX with the hydroxyl radical slightly increases with pH rise.展开更多
Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-ste...Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-steady state assumption.Effects of hydration temperature,product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics.The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions.When acrylamide concentration was higher than 250 g·L1,the deactivation of NHases became serious and the bi-steady state assumption was not applicable.When the hydration temperature was controlled at a relatively higher level such as 28°C,the total deactivation rate constant was about 2.8-fold of that at 20°C.展开更多
Elovich, parabolic diffusion, power function and exponential equations were used to describe K desorptionkinetics of 12 soils in a constant electric field of electro-ultrafiltration (EUF). Results showed that the Elov...Elovich, parabolic diffusion, power function and exponential equations were used to describe K desorptionkinetics of 12 soils in a constant electric field of electro-ultrafiltration (EUF). Results showed that the Elovich,parabolic diffusion and power function equations could describe K desorption kinetics well owing to their highcorrelatfon coefficients and low standard errors; but the exponential equation was not suitable to be usedin this study due to its relatively low correlation coefficients and relatively high standard errors. This workestablished successfully the relationships between the constants (slope or intercept) of kinetic equations andthe barley responses to K fertilizer in the multiple-site field experiments and K-supplying status of soils, theconstants of Elovich, parabolic diffusion and power function equations were very significantly or significantlycorrelated to the soil available K, relative yield of barley and K uptake of barley in NP plot. It was suggestedthat the kinetic equation constants could be used to estimate K-supplying power of soils.展开更多
The boron adsorption kinetic experiment in soil by means of a flow displacement technique showed that the kinetic data could be described with some mathematic equations. The average values of the correlation coefficie...The boron adsorption kinetic experiment in soil by means of a flow displacement technique showed that the kinetic data could be described with some mathematic equations. The average values of the correlation coefficient for zero-order, first-order, parabolic diffusion, Elovich, power function and exponential equations were 0.957, 0.982, 0.981, 0.984, 0.981 and 0.902, respectively. The correlation between adsorbed boron or its other expression form and time were the highest for first-order, parabolic diffusion, Elovich, and power function equations, the second for the zeroorder equation, and the lowest for the exponential equation. The parabolic diffusion equation fitted well the experimental results, with the least standard error among the six kinetic equations, showing that the movement of boron from soil solution to soil colloid surface may be controlled by boron diffusion speed. The boron content of rape seedling obtained from soil cultivation was correlated with the rate constants of the kinetic equations. The constants of first-order, parabolic diffusion,and exponential equations were significantly correlated with the boron content of the crop of NPK treatment at a 95% probability level, with correlation coefficients being 0.686, 0.691 and 0.641, respectively. In the case of zero-order equation, it was significant at 99% probability level (r =0.736). These results showed that the absorption kinetic constants of soil boron were closely related with the rape plant response to boron.展开更多
In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides ...In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction,the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting,the reaction order between organic sulfide and sulfone,the intrinsic oxidation rate constant of organic sulfide and sulfone,and the equilibrium constant between sulfone in model diesel and extractive solvent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.展开更多
The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This p...The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry ( DSC ) , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.展开更多
The dynamic recrystallization behavior of high strength steel during hot deformation was investigated.The hot compression test was conducted in the temperature range of 950-1150 °C under strain rates of 0.1,1 and...The dynamic recrystallization behavior of high strength steel during hot deformation was investigated.The hot compression test was conducted in the temperature range of 950-1150 °C under strain rates of 0.1,1 and 5 s-1.It is observed that dynamic recrystallization(DRX) is the main flow softening mechanism and the flow stress increases with decreasing temperature and increasing strain rate.The relationship between material constants(Q,n,α and ln A) and strain is identified by the sixth order polynomial fit.The constitutive model is developed to predict the flow stress of the material incorporating the strain softening effect and verified.Moreover,the critical characteristics of DRX are extracted from the stress-strain curves under different deformation conditions by linear regression.The dynamic recrystallization volume fraction decreases with increasing strain rate at a constant temperature or decreasing deformation temperature under a constant strain rate.The kinetics of DRX increases with increasing deformation temperature or strain rate.展开更多
This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the para...This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the parameter range of this study the europium reduction speed up with the increase of the system's temperature,the stirring intensity,feed concentration and the cathod area,and with the decrease of the cathodic potential.As the feed acidity increases,the reduction rate decreases.An empirical formula for europium's electroreduction kinetics in this experimental condition is also given.展开更多
The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in...The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in reasonable agreement with the experimental data (222.2±3kJ/mol). The calculated results show that the decomposition is a concerted process with hydrogen transferring and bond breaking via a five-membered cyclic transition state. The thermal rate constants of the decomposition are obtained by calculating microcanonical probability fluxes through transition state1.展开更多
The influence of four kinds of Schiff bases on a strain of Escherichia coli was studied by microcalorimetry. Differences in their capabilities of suppressing the metabolism of this bacterium were observed. The results...The influence of four kinds of Schiff bases on a strain of Escherichia coli was studied by microcalorimetry. Differences in their capabilities of suppressing the metabolism of this bacterium were observed. The results show that the extent and duration of the inhibitory effect on the metabolism as judged from the multiplication rate constant, k , varies with different Schiff bases. The multiplication rate constant k , of Escherichia coli (in log phase) in the presence of Mo salicylioaldehyde thiadizole, Mo piperonaldehyde thiosemicarbazone and Mo 3 methoxy salicylicaldehyde thiadizole decreases with the increase of concentrations of compounds c , and the relationships between k and c , maximum heat production rate p m and c , peak time of growth curves t p and c are of linearity. For Mo 6 nitro pieronalde thiosemicarbazone, the multiplication rate constant is constant irrespective of variation in concentration. The sequence of antibiotic activity of Schiff base is : Mo salicylioaldehyde thiadizole>Mo 3 methoxy salicylicaldehyde thiadizole>Mo piperonaldehyde thiosemicarbazone>6 nitro pieronalde thiosemicarbazone.展开更多
Kinetics of a chemical reaction provides an important means of determining the extent of the reaction and in reactor designs. Transesterification of jatropha oil with methanol and sodium hydroxide as a catalyst was co...Kinetics of a chemical reaction provides an important means of determining the extent of the reaction and in reactor designs. Transesterification of jatropha oil with methanol and sodium hydroxide as a catalyst was conducted in a well mixed reactor at different agitation speeds between 600 and 800 rpm and temperature range between 35°C and 65°C. The effect of variation of temperature and mixing intensity on rate constants were studied. The initial mass transfer controlled stage was considered negligible using the above impeller speeds and second order mechanism was considered for the chemically controlled kinetic stage. Samples were collected from the reaction mixture at specified time intervals and quenched in a mixture of tetrahydrofuran (THF) and sulphuric acid. The mixture was centrifuged at 2000 rpm for 15 minutes and the methyl ester was separated from the glycerol. The ester was washed with warm water (50°C), dried and analysed using gas chromatography coupled with flame ionization detector (GC/FID) to determine free and total glycerine and methyl ester. A mathematical model was fitted using second order rate law. High temperature and high mixing intensity increased reaction rates. The model fitted well with a high correlation coefficient (R2) of 0.999.展开更多
文摘This study was performed in two phases of work.In the first stage,four conventional first-order flotation kinetics models were fitted to the measured recoveries data and the best model were selected.In the second stage,influence of pH,solid concentration,water chemistry and the amount of collector dosage were investigated on kinetics parameters including flotation rate constant and ultimate recovery.The results indicated that that perfectly mixed reactor model and Kelsall model gave the best and the weakest fit to the experimental data,respectively.It was observed that flotation rate constant and ultimate recovery were strongly affected by chemical factors investigated especially water quality.The flotation rate constant decreased with increasing the solids content,while ultimate recovery increased to certain value and thereafter reduced.It was also found that the most values of flotation rate constant and ultimate recovery obtained in dosage of collector are 30 and 40 g/t,respectively.
基金Supported by the National Natural Science Foundation of China(51174184)National Basic Research Program of China(2012CBA01202)+3 种基金the Key Research Programof the Chinese Academy of Sciences(KGZD-EW-201-1)the Science and Technology Planof Nantong City(BK2013030)the University Science Research Project of Jiangsu Province(14KJB150019)Open Subject of Changchun Institute of Applied Chemistry,Chinese Academy of Sciences(RERU2014016)
文摘The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12](tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated using a constant interfacial cell with laminar flow. The effects of stirring speed, temperature and specific interfacial area on the extraction rate were examined. The results indicate that mass transfer kinetics of La(III) is a mixed-controlled process influenced by interfacial reaction. On the basis of mass transfer kinetic results in the extraction of La(III) by [A336][CA-12], the extraction rate equation of La(III) is proposed in terms of pseudo-firstorder constants, which is supported by the measured thermodynamic equations. The mass-transfer kinetic model deduced from the rate controlling step is adequate to interpret the experimental data qualitatively.
基金financial support from the National Natural Science Foundation of China (21838004)Priority Academic Program Development of Jiangsu Higher Education Institutions (PPZY2015A044)Top-notch Academic Programs Project of Jiangsu Higher Education Institution (TAPP)。
文摘Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents causes problems such as slow crystallization rate and small crystal size,limiting the recovery rate and economic value of the MAP.The present study was conducted to investigate the effects of concentrations of three heavy metal ions(Cu^(2+),Zn^(2+),and Pb^(2+))on the crystal morphology,crystal size,average growth rate,and crystallization kinetics of MAP.A relationship was established between the kinetic rate constant Ktcalculated by the chemical gradient model and the concentrations of heavy metal ions.The results showed that low concentrations of heavy metal ions in the solution created pits on the MAP surface,and high level of heavy metal ions generated flocs on the MAP surface,which were composed of metal hydroxides,thus inhibiting crystal growth.The crystal size,average growth rate,MAP crystallization rate,and kinetic rate constant Ktdecreased with the increase in heavy metal ion concentration.Moreover,the Ktdemonstrated a linear relationship with the heavy metal concentration ln(C/C~*),which provided a reference for the optimization of the MAP crystallization process in the presence of heavy metal ions.
基金Supported by the National Natural Science Foundation of China(51574213,51074150)the Key Project of Chinese National Programs for Fundamental Research and Development(2012CBA01203,2013CB632602)
文摘A novel constant interfacial area cell(NCIAC),by spatially separating the agitation from liquid flow circulation of organic and aqueous two phases,was suggested to obtain detailed kinetic data for Er(Ⅲ) extraction from chloride medium by 2-ethyl-hexyl-phosphonic acid mono-(2-ethylhexyl) ester(EHEHPA).Different from the traditional Lewis cell and the constant interfacial area cell with laminar flow,the concentrations of Er(Ⅲ) in organic and aqueous two phases were uniform,and the stability of the interfacial area between the two phases could be controlled effectively.Therefore,the special requirements for the design of agitators in the traditional Lewis cell and the constant interfacial area cell for minimizing the influence of diffusion resistance could be avoided.Experimental results indicated that the extraction kinetics was mainly affected by the aqueous flow rate,interfacial area between organic and aqueous two phases,and the aqueous p H values.An extraction kinetic equation was suggested based on the experimental data.
文摘A technique was developed to study mass trans fer process and inter facial reaction in two phases system. This constant inter facial cell with a laminar flow was made into a cubic structure. The two fluids were continuously recycled and mixed. The concentration of each liquid could be monitored by two different methods. This kind of structure made both flows near the inter face flow parallel to the inter face. The inter face was smooth and steady. The mass trans fer rate could be judged by the linear velocity of the flows. The technique can be used for the analyses of the control step in both phases near the inter face in a diffusion control process. A preliminary hydrodynamics and mass trans fer study on the cell was presented, which ensures the distinguishing between a diffusion and a chemical reaction control process. A simplified mass transfer equation,N =0.5303D 1 /2* (Ci- Cb)* (V / B) 1/2, was achieved.
基金Project (2012CBA01202) supported by the National Basic Research Program of ChinaProject (51174184) supported by the National Natural Science Foundation of China+2 种基金Project (KGZD-EW-201-1) supported by the Key Research Program of the Chinese Academy of SciencesProject (BK2013030) supported by Science and Technology Plan of Nantong City,ChinaProject (RERU2014016) supported by Open Subject of Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,China
文摘The extraction kinetics of Ce(Ⅳ) and Ce(Ⅳ)-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]([trialkylmethylammonium][di-2-ethylhewanxylphosphinate]) with a constant interfacial area cell with laminar flow were studied,just to elucidate the extraction mechanism and the mass transfer models.The data were analyzed in terms of pseudo-first-order constants.The effects of stirring speed,specific interfacial area and temperature on the extraction rate in both systems were discussed,suggesting that the extractions were mixed bulk phases-interfacial control process.Supported by the experimental data,the corresponding rate equations for Ce(Ⅳ) extraction system and Ce(Ⅳ)-F^- mixture extraction system were obtained.The experimental results indicated the rate-controlling step.The kinetics model was deduced from the rate-controlling step and consistent with the rate equation.
文摘Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism: (a) 700-750°C, (b) 750-800°C, and (c) 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000°C), the dominant controlling mechanism is diffusion.
文摘The kinetics of the catalytic reforming reaction of methane with carbondioxide to produce synthesis gas on a Ni/α-Al_2O_3 and a HSD-2 type commercial catalyst has beenstudied. The results indicate that the reaction orders are one and zero for methane and carbondioxide, respectively, when the carbon dioxide partial pressure was about 12.5-30.0 kPa and thetemperature was at 1123-1173 K. However, when the carbon dioxide partial pressure was changed to30.0-45.0 kPa under the same temperature range of 1123-1173 K, the reaction orders of methane andcarbon dioxide are one. Furthermore, average rate constants at different temperatures weredetermined.
基金supported by Natural Science Foundation of China (Grant 50708067, 51078281)the Foundation for the Author of the National Excellent Doctoral Dissertation of China (Grant 2007B48)
文摘Objective To investigate the kinetic rate constants ozone and hydroxyl radicals towards two groups of antimicrobials --sulfadiazine (SD) and sulfamethoxazole (SMX).Methods The solute consumption method was used to detect the rate constants of ozone alone with sulfadiazine and sulfamethoxazole, and tertiary butanol was selected as a scavenging agent and pH was adjusted to 2.5 by adding orthophosphate buffers (OB); and the competition kinetics studying methodwith nitrobenzene as a reference was applied to measure the rate constants of hydroxyl radicals towards sulfadiazine and sulfamethoxazole, and oH was adjusted to 7.0 bv adding OB.Results The rate constants of SD and SMX with ozone alone were 261 mol^-1· dm^3 · s^-1 and 303 mol^-1· dm3 · s-1 by calculating in low reaction system. The rate constants of hydroxyl radicals with SD and SMX were 2.2×1010 mol^-1 · dm^3 · s^-1 and 2.7×1010 mol^-1· dm^3 · s^-1, respectively. Moreover, the rate constants of hydroxyl radicals with SMX were found to have increased from 3.6×109 mol^-1· dm^3 · s^-1 to 2.8×1010 mol^-1· dm^3 · s^-1 with pH value rising from 5.0 to 7.8. Conclusion SMX and SD are both refractory to ozone oxidation alone, and are liable to be degraded by hydroxyl radicals, and the rate constants of SMX with the hydroxyl radical slightly increases with pH rise.
基金Supported by the Foundation for the Authors of National Excellent Doctoral Dissertation of China (200345)the National High Technology Research and Development Program of China (2007AA02Z201)the National Basic Research Program of China (2007CB714304)
文摘Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-steady state assumption.Effects of hydration temperature,product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics.The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions.When acrylamide concentration was higher than 250 g·L1,the deactivation of NHases became serious and the bi-steady state assumption was not applicable.When the hydration temperature was controlled at a relatively higher level such as 28°C,the total deactivation rate constant was about 2.8-fold of that at 20°C.
文摘Elovich, parabolic diffusion, power function and exponential equations were used to describe K desorptionkinetics of 12 soils in a constant electric field of electro-ultrafiltration (EUF). Results showed that the Elovich,parabolic diffusion and power function equations could describe K desorption kinetics well owing to their highcorrelatfon coefficients and low standard errors; but the exponential equation was not suitable to be usedin this study due to its relatively low correlation coefficients and relatively high standard errors. This workestablished successfully the relationships between the constants (slope or intercept) of kinetic equations andthe barley responses to K fertilizer in the multiple-site field experiments and K-supplying status of soils, theconstants of Elovich, parabolic diffusion and power function equations were very significantly or significantlycorrelated to the soil available K, relative yield of barley and K uptake of barley in NP plot. It was suggestedthat the kinetic equation constants could be used to estimate K-supplying power of soils.
文摘The boron adsorption kinetic experiment in soil by means of a flow displacement technique showed that the kinetic data could be described with some mathematic equations. The average values of the correlation coefficient for zero-order, first-order, parabolic diffusion, Elovich, power function and exponential equations were 0.957, 0.982, 0.981, 0.984, 0.981 and 0.902, respectively. The correlation between adsorbed boron or its other expression form and time were the highest for first-order, parabolic diffusion, Elovich, and power function equations, the second for the zeroorder equation, and the lowest for the exponential equation. The parabolic diffusion equation fitted well the experimental results, with the least standard error among the six kinetic equations, showing that the movement of boron from soil solution to soil colloid surface may be controlled by boron diffusion speed. The boron content of rape seedling obtained from soil cultivation was correlated with the rate constants of the kinetic equations. The constants of first-order, parabolic diffusion,and exponential equations were significantly correlated with the boron content of the crop of NPK treatment at a 95% probability level, with correlation coefficients being 0.686, 0.691 and 0.641, respectively. In the case of zero-order equation, it was significant at 99% probability level (r =0.736). These results showed that the absorption kinetic constants of soil boron were closely related with the rape plant response to boron.
文摘In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction,the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting,the reaction order between organic sulfide and sulfone,the intrinsic oxidation rate constant of organic sulfide and sulfone,and the equilibrium constant between sulfone in model diesel and extractive solvent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.
文摘The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry ( DSC ) , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.
基金Project (51322405) supported by the National Natural Science Foundation of ChinaProject (CX2013B085) supported by Hunan Provincial Innovation Foundation for Postgraduate,China
文摘The dynamic recrystallization behavior of high strength steel during hot deformation was investigated.The hot compression test was conducted in the temperature range of 950-1150 °C under strain rates of 0.1,1 and 5 s-1.It is observed that dynamic recrystallization(DRX) is the main flow softening mechanism and the flow stress increases with decreasing temperature and increasing strain rate.The relationship between material constants(Q,n,α and ln A) and strain is identified by the sixth order polynomial fit.The constitutive model is developed to predict the flow stress of the material incorporating the strain softening effect and verified.Moreover,the critical characteristics of DRX are extracted from the stress-strain curves under different deformation conditions by linear regression.The dynamic recrystallization volume fraction decreases with increasing strain rate at a constant temperature or decreasing deformation temperature under a constant strain rate.The kinetics of DRX increases with increasing deformation temperature or strain rate.
基金The project was supported by the National Natural Science Foundation of China
文摘This article studied the europium electroreduction kinetic properties in the Sm-Eu-Gd chloride system by using an electrolytic cell with membrane and constant potential method.The results indicate that within the parameter range of this study the europium reduction speed up with the increase of the system's temperature,the stirring intensity,feed concentration and the cathod area,and with the decrease of the cathodic potential.As the feed acidity increases,the reduction rate decreases.An empirical formula for europium's electroreduction kinetics in this experimental condition is also given.
文摘The mechanism and kinetics for the decomposition of 3-hydroxy-3-methyl-2-butanone have been studied by using the ab initio RHF/3-21G method. The calculated activation barrier of the reaction is 249.6kJ/mol which is in reasonable agreement with the experimental data (222.2±3kJ/mol). The calculated results show that the decomposition is a concerted process with hydrogen transferring and bond breaking via a five-membered cyclic transition state. The thermal rate constants of the decomposition are obtained by calculating microcanonical probability fluxes through transition state1.
文摘The influence of four kinds of Schiff bases on a strain of Escherichia coli was studied by microcalorimetry. Differences in their capabilities of suppressing the metabolism of this bacterium were observed. The results show that the extent and duration of the inhibitory effect on the metabolism as judged from the multiplication rate constant, k , varies with different Schiff bases. The multiplication rate constant k , of Escherichia coli (in log phase) in the presence of Mo salicylioaldehyde thiadizole, Mo piperonaldehyde thiosemicarbazone and Mo 3 methoxy salicylicaldehyde thiadizole decreases with the increase of concentrations of compounds c , and the relationships between k and c , maximum heat production rate p m and c , peak time of growth curves t p and c are of linearity. For Mo 6 nitro pieronalde thiosemicarbazone, the multiplication rate constant is constant irrespective of variation in concentration. The sequence of antibiotic activity of Schiff base is : Mo salicylioaldehyde thiadizole>Mo 3 methoxy salicylicaldehyde thiadizole>Mo piperonaldehyde thiosemicarbazone>6 nitro pieronalde thiosemicarbazone.
文摘Kinetics of a chemical reaction provides an important means of determining the extent of the reaction and in reactor designs. Transesterification of jatropha oil with methanol and sodium hydroxide as a catalyst was conducted in a well mixed reactor at different agitation speeds between 600 and 800 rpm and temperature range between 35°C and 65°C. The effect of variation of temperature and mixing intensity on rate constants were studied. The initial mass transfer controlled stage was considered negligible using the above impeller speeds and second order mechanism was considered for the chemically controlled kinetic stage. Samples were collected from the reaction mixture at specified time intervals and quenched in a mixture of tetrahydrofuran (THF) and sulphuric acid. The mixture was centrifuged at 2000 rpm for 15 minutes and the methyl ester was separated from the glycerol. The ester was washed with warm water (50°C), dried and analysed using gas chromatography coupled with flame ionization detector (GC/FID) to determine free and total glycerine and methyl ester. A mathematical model was fitted using second order rate law. High temperature and high mixing intensity increased reaction rates. The model fitted well with a high correlation coefficient (R2) of 0.999.